Photographic products, processes and compositions



radicals each R may be a hydrogen,

r 3,212,167 Patented Feb. 20, 1962 PHOTOGHIC PRODUCTS, PRQCESSES .AND COWOSITIONS vMilton Green, Newton Highlands, Mass,

Polaroid Corporation, Cambridge, Mass,

tion of Delaware No'Drawing. Filed Mar. 28, 1957, Ser. No.

' 7 Claims. (Cl. 96-61) assignor to a corpora- This invention relates to novel chemical compounds and more particularly to certain novel chemical compounds useful as photographic developing and antistain agents 7 and products and processes utilizing said compounds.

One object of this invention is to provide novel chemical compounds and suitable syntheses for their preparation.

Another object of the invention is to provide novel photographic developing agents which possess various rates of mobility, and compositions containing them, for

the development of silver halide emulsions.

- A further object is to provide novel photographic antistain agents for use in color processes.

Other objects of this invention will in ,and will in part appear hereinafter.

The invention accordingly comprises the several steps 7 and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions. possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure and the scope of the application of which willbe indicated in the claims.

The following detailed description will give a fuller understanding ofthe nature and objects of the invention.

The novel compounds of this invention may be represented by the formulae:

part be obvious (I) tl-m) (X)m C-N n X C-N- R (l is 2 wherein R is a bivalent hydrocarbon radical, and is preferably an arylene or aralkarylene radical; each R may be a hydrogen, alkyl, or aryl radical; Q may be a single valence bond, i.e., a covalent bond, or a bivalent hydrocarbon radical; m is a positive integer from 1 to 5 inclusive and preferably 3; each D may be a hydrogen or alkyl ,group; and each X is selected from the group consisting of carboxyl, i.e.

- radicals provided that at least one X is a gY-m-N-o radical. In the I a l, or y p; each R may be a single valence bond, i.e., a covalent bond, ora bivalent hydrocarbon radical and each Y is a 2,5-dihydroxyphenyl, a 2,3-dihydroxyphenyl, or a 3,4-dito hydrocarbon groups wherein and aralk-arylene groups such as As examples of the v V r radical in the above formulae, mention may be made of the following: a

. o H OH on 2) O l I -i-N-OH2CH JE-NQQmOE-C? on ti --N When Q in the above definition is a covalent bond, the

' compounds are derived from oxalic acid.

In the preferred embodiment R is a diphenyl-methane radical and m is a number from 1 to 3. Such compounds may be represented by the formula:

ts-m) wherein D, X and R have the same meaning as above. One method of preparing compounds within the scope of this invention is by condensing two mols of a suitable acid chloride, said acid chloride being at least dibasic,

e.g., pyromellityl chloride, with one mol of a dibasic amine and reacting the free acyl chloride radicals, i.e.,

radical, e.g., p-aminophenethyl-hydroquinone or a mixture 1 of p-aminophenethyl-hydroquinone and p-aminophenylhydroquinone. The amine salts may also be used.

7 'Another method of preparing compounds within the scope of this vention is by condensing two mols of a diacid, etc., with one mol of a ing, and drying,'4.5

3 basic acid anhydride, e.g., phthalic anhydride, with one 'mol of a dibasic amine and reacting the free carboxyl radicals of the intermediate with an excess of a suitable amine or mixture of amines containing the appropriate -R -Y radical. I

Still another method of preparing compounds within the scope of the invention is by condensing two mols of an acid which is at least dibasic, e.g., oxalic acid, sebacic dibasic amine and reacting the free carboxyl radicals of the intermediate with an excess of a suitable amine or mixture of amines containing the appropriate Y radical.

As examples of suitable dibasic amines useful in the above preparations, mention may be made of 4,4'-diaminodiphenylmethane, p-phenylene diamine, etc.

The following example illustrates the preparation of compounds within the scope of'this invention, and particularly the preferred embodiment, illustration only:

Example I 0.3 gm. of diaminodiphenylmethane is added to 1 gm.

7 of pyrromellityl chloride in 25 cc. of pyridine and the solution is refluxed for one-half hour. 10 gms. of paminophenethyl-hydroquinone-0,0'diacetate solved in 35 cc. of pyridine is added to the above solution and it is refluxed'for an additional one-half hour and cooled. The reaction product is separated by precipitating in a hydrochloric acid-ice bath.

a The tan precipitate is filtered and the acetate radicals are hydrolyzed off, under partial vacuum, by subjecting the precipitateto an aqueous ethanol solution of sodium hydroxide over a steam bath for a few minutes.

The reaction product is cooled and then precipitated by adding dilute hydrochloric acid. Upon filtering, washg'ms. of a developer having the probable formula:

01120110 NEE-( 0 CHaCHQNH-E LOH is obtained, and this product may be described as 4,4'-bis- [2",4",5"-tri-(p-[2',5' dihydroxyphenethyl] phenylcarbamyl) -benzamido]-dipheny1methane.

It will he noted that in the above example and in other preparations wherein at least dibasic and preferably tribasic, tetrabasic, etc., acids and acid chlorides are used that polymeric compounds may be obtained by increasing the amount of dibasic amine so that the molar ratio of amine to acid will approach 1. i

As pointed out previously, the novel compounds of this invention are useful as developing agents for silver halide emulsions. As an example of a suitable developing composition utilizing one of the novel compounds of this inand is given as an hydrochloride disvention, mention may be made of the following composition:

yll-phenylcarbarnyl) benzamido] -fdiphenyl'meth- V V k It will be understood that it is within the scope of this invention to varythe developerv composition illustrated above. The percentage of ingredients may be varied to suit particular needs. Mixtures of the novel developing agents may be used. If the composition is to bev applied to the emulsion by being spread thereon, in a thinlayer, it may also include a film-forming thickening agent such, for example, as a high molecular weight polymer, e.g., sodium carboxymethyl cellulose.

Further, the use of the developing agents of this invention is in no way restricted to incorporating them into developing compositions; where desired they may be employed in photosensitive elements, c.g., by placing them in or behind a silver halide 'emulsion layer.

emulsion with As noted previously,

vention possess various rates of mobility in photographic processes.

vversely withthe number'of amide groups in In general the relative rate of mobility of com the invention willvary inv the'molecule.

The developingagents which possess relatively higher mobility are useful in ditfusiomtransfer reversal processes, both dye and silver, and are especially useful in such photographic processes wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver pounds within the scope of compositions of this invention may have incorporated therein as a further-ingredient a silver halide solvent such as sodium thiosulfate. Thus by adding sodium thiosulfate When so placed they, may be made functional by permeating said to the composition illustrated above and using an image- "'-dihydroxyphenethyl]-phenylcarbamyl) benzamido]- receiving element in conjunction with the photosensitive diphenylmethane. element a transfer image may be obtained. 4. A photographic product comprising a support, said The novel developing agents of this invention which support bearing on one surface a plurality of layers inpossess relatively low mobility are especially useful in 5 cluding a silver halide emulsion layer, at least one of said photographic diifusion-transfer processes in which it is layers containing at least one compound selected from desirable to exclude the developing agent from the imagethe group of compounds Within the formula:

receiving element or where it is desired to substantially wherein R is a methylene group, R is a phenethyl group, prevent the developer from wandering from a particular in which the ethyl group of said phenethyl group is linked portion of the photosensitive element. Such low mobility to the Y radical and Y is selected from the group condevelopers are particularly useful in the processes dissisting of ortho-dihydroxyphenyl and para-dihydroxyclosed and claimed in the copending application of Howphenyl radicals.

.ard G. Rogers, Serial No. 599,122, filed July 20, 1956. 5. A photographic product comprising a support, said In multilayer color processes, where antistain agents support bearing on one surface a plurality of layers inwhich are relatively immobile are required, the novel low eluding a silver halide emulsion layer, at least one of said mobility compounds of this invention are again useful. lay rs con ain ng 4,4'-bis-[2,4,5"-tri-(p-[2"',5"-dihy- The novel compounds of this invention are further useroxyp n hyll-ph ny r my )-benzamido] dipheuylful as antioxidants in petroleum products, etc. They th eare also useful as intermediates, 6. A process of developing an exposed silver halide Since certain changes may be made in the above prodemulsion, s pr comprising treating said emulsion uct, processes and compositions without departing from fo a u i t time tqdevelop he latent image to silver the scope of the invention herein involved, it is intended f an aqueous $0111t1011 comprising an alkaline malethat all matter contained in the above description shall be ri l and at leastplie compound selected from the group interpreted as illustrative and not in a limiting sense. of compounds within the formula:

I I Y-Bfl-NH-C o-NH R NH fit 3-NH-R-Y til ll 0 Li What is claimed is: wherein R is a methylene group, R is a phenethyl group,

1. As a photographic developer composition for the the ethyl substituent of said phenethyl group being linked formation of silver transfer prints, an aqueous solution to the Y radical and Y is selected from the group concomprising an alkaline material, a silver halide solvent, sisting of ortho-dihydroxyphenyl and para-dihydroxyphensaid solvent being capable of forming a soluble complex yl radicals. with silver halide, at least one compound selected from A method of developing an exposed Silver halide the group of compounds within the formula: emulsion which comprises treating said emulsion with an in .ii t it i R wherein R is a methylene group, R is a phenethyl group, aqueous solution comprising an alkaline material and the ethyl substituent of said phenethyl group being linked bis -(P-l y YP Y to the Y radical is selected from the group consisting of pheuylcarbamyl) benzamido] diphenylrnethane for a ortho-dihydroxyphenyl and para-dihydroxyphenyl radi- Sufiiciellt e to develop the latent image to Sill/e1- cals.

2. A composition as defined in claim 1 including a References Cited in the file of this Patet film-forming, viscosity-increasing agent. 5 UNITED STATES PATENTS 3. As a novel photographic developer composition for 2,515,147 Wasley July 11 1950 the formation of silver transfer prints, an aqueous solu- 2,610,122 J h et a1, Sept 9, 5 tion comprising an alkaline material, a silver halide sol- 2,570,374 c i 23 1954 vent, said solvent being capable of forming a soluble com- 2,713,594 Sauer July 19, 1955 plex with silver halide, and 4,4'-bis-[2",4",5"-tri-(p-[2",- 2,735,765 Loria et al. Feb. 21, 1956 

1. AS A PHOTOGRAPHIC DEVELOPER COMPOSITION FOR THE FORMATION OF SILVER TRANSFER PRINTS, AN AQUEOUS SOLUTION COMPRISING AN ALKALINE MATERIAL, SILVER HALIDE SOLVENT, SAID SOLVENT BEING CAPABLE OF FORMING A SOLUBLE COMPLEX WITH SILVER HALIDE, AT LEAST ONE COMPOUND SELECTED FROM THE GROUP OF COMPOUNDS WITHIN THE FORMULA: 